Monazo pigments containing hydroxynaphthoylaminobenzimidazalone radical

ABSTRACT

The instant invention relates to monoazo pigments containing a hydroxynaphthoylaminobenzimidazolone radical of the following formula ##STR1## These pigments are useful for coloring high molecular weight materials in orange to brown shades of especially good fastness properties.

The present invention relates to valuable new monoazo pigments of theformula I ##STR2## wherein Z represents a --CO-- or --SO₂ -- group,

Q represents a hydrogen atom, a bromine atom or a methoxy group,

R represents an alkyl group of 1 to 4 carbon atoms which isunsubstituted or substituted by a chlorine atom or an alkoxy group of 1to 4 carbon atoms, or represents a group of the formula ##STR3## whereinY₁ represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1to 4 carbon atoms,

Y₂ and Y₃, each independently of the other, represents a hydrogen orchlorine atom, a trifluoromethyl group, an alkyl or alkoxy group of 1 to4 carbon atoms, an alkanoylamino group of 2 to 4 carbon atoms or thegroup --COOR₁, wherein

R₁ represents an alkyl group of 1 to 4 carbon atoms which isunsubstituted or substituted by halogen atoms or alkoxy groups of 1 to 4carbon atoms; a cycloalkyl group of 5 to 6 carbon atoms, a benzyl group,or a phenyl group which is unsubstituted or substituted by halogen atomsor alkyl or alkoxy groups of 1 to 4 carbon atoms, or

Y₂ and Y₃ together represent a fused benzene ring which is unsubstitutedor substituted by chlorine,

X₁ represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1to 4 carbon atoms, an alkoxycarbonyl group of 2 to 4 carbon atoms or aphenoxy group,

R₂ represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms ora phenyl radical which is unsubstituted or substituted by halogen atoms,alkyl or alkoxy groups of 1 to 4 carbon atoms,

X₂ represents a hydrogen or halogen atom, an alkyl or alkoxy group of 1to 4 carbon atoms or a phenoxy group,

n is 1 or 2, and

Z₁ represents a group of the formula --OCH₂ --, ##STR4## --CONH-- or--NH--, with the proviso that, if R₂ represents alkyl or phenyl, atleast one of the symbols Y₁, Y₂ or Y₃ may not represent hydrogen, and ifR represents alkyl, R₂ must represent hydrogen.

Alkyl group substituents are for example methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl or tert-butyl, but preferably methyl orethyl.

Alkoxy group substituents are for example methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy or tert-butoxy, but especially methoxy and ethoxy.

An alkoxycarbonyl group X₁ is for example a methoxycarbonyl,ethoxycarbonyl, n-propoxycarbonyl or isopropoxycarbonyl group, butpreferably a methoxycarbonyl group.

An alkanoylamino group represented by Y₂ and Y₃ is for example anacetylamino, propionylamino, n-butyrylamino or isobutyrylamino group,but preferably the acetylamino group.

A chloroalkyl group R is a chloroalkyl group containing 1 or 2 chlorineatoms and 1 to 4 carbon atoms, for example chloromethyl, chloroethyl,chloro-n-propyl, chloroisopropyl, chloro-n-butyl, chloro-tert-butyl,dichloroethyl, dichloropropyl, dichloro-n-butyl, but especiallychloroethyl and chloro-n-propyl.

The alkoxy moiety of an alkoxyalkyl group R can contain 1 to 4 carbonatoms, for example in methoxyethyl, ethoxyethyl, propoxyethyl,isopropoxyethyl, n-butoxyethyl, tert-butoxyethyl, and the alkyl moietyis in particular ethyl. Such a group is preferably methoxyethyl orethoxyethyl.

A cycloalkyl group R₁ is for example a cyclopentyl group, but isespecially a cyclohexyl group.

A substituted phenyl group R₁ is for example mono-, di- ortrichlorophenyl, tolyl, xylyl, or mesitilenyl, ethylphenyl,tert-butylphenyl, diethylphenyl, triethylphenyl, methoxyphenyl,dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, propoxyphenyl,methoxycarbonylphenyl, ethoxycarbonylphenyl, dimethoxycarbonylphenyl,acetylaminophenyl, propionylaminophenyl, isobutyrylaminophenyl, and thesubstituents are especially in the ortho- or para-position and, in thecase of monosubstituted phenyl, preferably in the para-position. Asubstituted phenyl group R₁ is preferably p-chlorophenyl or p-tolyl.

A substituted phenyl radical R₂ is for example mono- di- ortrichlorophenyl, tolyl, xylyl or mesityl, ethylphenyl, tert-butylphenyl,diethylphenyl, triethylphenyl, methoxyphenyl, dimethoxyphenyl,trimethoxyphenyl, ethoxyphenyl, propoxyphenyl, and the substituents areespecially in the ortho- and para-position and, in the case ofmono-substituted phenyl, preferably in the para-position. A substitutedphenyl group R₂ is preferably p-chlorophenyl or p-tolyl.

Particularly interesting monoazo pigments are those of the formula II##STR5## wherein Z, Y₁, Y₂ and Y₃ have the above meanings,

R₃ represents hydrogen or methyl,

X₄ represents chlorine, methyl, methoxy, methoxycarbonyl orethoxycarbonyl, and

X₅ represents hydrogen, chlorine, methyl or methoxy, with the provisothat, if R₃ is methyl, at least one of the symbols Y₁, Y₂ or Y₃ may notrepresent hydrogen.

Particularly preferred monoazo pigments are those of the formula III##STR6## wherein R₃, X₄, X₅ and Z have the above meanings and R₄represents an alkyl group of 1 to 4 carbon atoms, a benzyl group, or aphenyl group which is unsubstituted or substituted by chlorine atoms oralkyl or alkoxy groups of 1 to 4 carbon atoms.

Preferred monoazo pigments are also those of the formula IV ##STR7##wherein R₃, X₄, X₅, Z and n have the above meanings and X₆ represents ahydrogen or chlorine atom.

Particularly interesting monoazo pigments are also those of the formulaV ##STR8## wherein X₄ and X₅ have the given meanings and R₅ representsan alkyl group of 1 to 4 carbon atoms, as well as those of the formulaVI ##STR9## wherein R₅ and X₅ have the given meanings and X₇ representsmethyl or methoxy.

The monoazo pigments of the formula I are obtained by

(a) coupling the diazo compound of an amine of the formula VII ##STR10##wherein R, Z and X₁ have the above meanings, with a naphthoic arylide ofthe formula VIII ##STR11## wherein Q, R₂, Z₁ and X₂ have the abovemeanings, or

(b) condensing an azocarboxylic halide of the formula IX ##STR12##wherein Q, R, Z and X₁ have the above meanings, with an amine of theformula X ##STR13## wherein R₂, Z₁ and X₂ have the above meanings.

Examples of diazo components are:

1-amino-2-chlorobenzene-5-carboxylic acid 4'-methylphenyl ester

1-amino-2-methoxybenzene-5-carboxylic acid 4'-methylphenyl ester

1-amino-2-methylbenzene-5-carboxylic acid phenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 2'-chlorophenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 4'-chlorophenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 2',4'-dichlorophenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 2',4',5'-trichlorophenyl ester

1-amino-2-chlorobenzene-5-carboxylic acid 2'-methylphenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 4'-methylphenyl ester

1-amino-2-chlorobenzene-5-carboxylic acid 4'-phenylphenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 4'-methoxyphenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 4'-chloro-2'-methylphenylester

1-amino-2-methylbenzene-5-carboxylic acid 4'-chloro-3'-methylphenylester

1-amino-2-methylbenzene-5-carboxylic acid 4'-isobutylphenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 3'-trifluoromethylphenyl ester

1-amino-2-methylbenzene-5-carboxylic acid 2'-chloroethyl ester

1-amino-chlorobenzene-5-carboxylic acid 2'-chloroethyl ester

2-amino-terephthalic acid diphenyl ester

3-amino-isophthalic acid diphenyl ester

1-amino-2-chlorobenzene-5-carboxylic acid 4'-chlorophenyl ester

1-amino-2-chlorobenzene-5-carboxylic acid β-naphthyl ester

1-amino-2-methoxybenzene-5-carboxylic acid 4'-chlorophenyl ester

1-amino-2-methoxybenzene-5-carboxylic acid 4'-methoxyphenyl ester

1-amino-2-phenoxybenzene-5-carboxylic acid 4'-methylphenyl ester

1-amino-2-chlorobenzene-5-sulphonic acid 4'-methoxyphenyl ester

1-amino-2-methylbenzene-5-sulphonic acid 4'-chlorophenyl ester

1-amino-2-methoxybenzene-5-sulphonic acid 4'-methylphenyl ester

1-amino-2-chlorobenzene-5-sulphonic acid phenyl ester

1-amino-2-methylbenzene-5-sulphonic acid phenyl ester

1-amino-2-methoxybenzene-5-sulphonic acid phenyl ester

3-amino-4-chlorobenzoic acid methyl ester

3-amino-4-chlorobenzoic acid ethyl ester

3-amino-4-methylbenzoic acid ethyl ester

3-amino-4-methylbenzoic acid isopropyl ester

3-amino-4-methylbenzoic acid β-chloroethyl ester

3-amino-4-methoxybenzoic acid methyl ester amonoterephthalic aciddimethyl ester aminoterephthalic acid diethyl ester

4-methyl-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester

4-chloro-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester

4-methoxy-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester

4-phenoxy-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 3'-methoxycarbonylphenyl ester

4-chloro-3-aminobenzoic acid 3'-methoxycarbonylphenyl ester

4-phenoxy-3-aminobenzoic acid 3'-methoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 4'-ethoxycarbonylphenyl ester

4-methoxy-3-aminobenzoic acid 3'-ethoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 3'-ethoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 4'-n-propoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 3'-n-propoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 4'-isopropoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 3'-isopropoxycarbonylphenyl ester

4-chloro-3-aminobenzoic acid 4'-isopropoxycarbonylphenyl ester

4-methoxy-3-aminobenzoic acid 4'-isopropoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 4'-benzyloxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 4'-β-chloroethoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 3'-β-chloroethoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 4'-n-butoxycarbonylphenyl ester

4-methyl-3-aminobenzoic acid 4'-isobutoxycarbonylphenyl ester.

The amines of the formula VII are advantageously obtained bycondensation of a nitrobenzoyl chloride or a nitrobenzenesulphonylchloride of the formula ##STR14## wherein X₁ and Z have the givenmeanings, with a compound of the formula

    HOR

wherein R has the given meaning, and reduction of the resulting nitroester to give the aminocarboxylate or aminobenzenesulphonate. Acatalytic reduction is preferably carried out.

The aminobenzenecarboxylates or aminobenzenesulphonates are diazotisedand coupled with the naphthalic arylides of the formula VIII.

The coupling components of the general formula VIII can be prepared byknown methods, for example by reacting 2-oxy-3-naphthoic chloride withthe corresponding amines.

Examples of such amines are:

5-amino-benzimidazolone

5-amino-1-methyl-benzimidazolone

5-amino-1-n-butyl-benzimidazolone

5-amino-1-phenyl-benzimidazolone

5-amino-1-p-chlorophenyl-benzimidazolone

5-amino-1-p-methylphenyl-benzimidazolone

5-amino-1-p-methoxyphenyl-benzimidazolone

5-amino-6-chloro-benzimidazolone

5-amino-6-bromo-benzimidazolone

5-amino-6-methyl-benzimidazolone

5-amino-6-methoxy-benzimidazolone

6-amino-2,4-dihydroxyquinazoline

7-amino-phenmorpholone-3

6-amino-phenmorpholone-3

7-amino-6-chloro-phenmorpholone-3

7-amino-6-methyl-phenmorpholone-3

7-amino-6-methoxy-phenmorpholone-3

6-amino-4-methyl-quinolone-2

7-amino-4-methyl-quinolone-2

7-amino-4,6-dimethyl-quinolone-2

6-amino-7-chloro-4-methyl-quinolone-2

7-amino-4-methyl-6-methoxy-quinolone-2

The cited heterocyclic compounds are known compounds. The diazotisationis carried out by known methods.

The coupling preferably takes place in a weakly acid medium,advantageously in the presence of conventional agents that promote thecoupling. As such coupling promoters there may be mentioned inparticular dispersants, for example aralkylsulphonates, such asdodecylbenzenesulphonate, or 1,1'-dinaphthylmethane-2,2'-disulphonicacid or polycondensation products of alkylene oxides. The dispersion ofthe coupling component can also advantageously contain protectivecolloids, for example methylcellulose or minor amounts of inert organicsolvents which are sparingly soluble or insoluble in water, for exampleoptionally halogenated or nitrated aromatic hydrocarbons, for example,benzene, toluene, xylene, chlorobenzene, dichlorobenzene ornitrobenzene, and also aliphatic halogenated hydrocarbons, for example,carbon tetrachloride or trichloroethylene, and furthermorewater-miscible organic solvents, for example acetone, methyl ethylketone, methanol, ethanol or isopropanol, or preferably dimethylformamide.

The coupling can also advantageously be carried out by continuouslycombining an acid solution of the diazonium salt with an alkalinesolution of the coupling component in a mixing nozzle, whereupon animmediate coupling of the component occurs. Care must be taken that thediazo component and the coupling component are present in equimolecularamounts in the mixing nozzle, and a slight excess of coupling componentproves to be advantageous. This is most simply achieved by controllingthe pH of the liquid in the mixing nozzle. Furthermore, intenseturbulent mixing of the two solutions in the mixing nozzle must beensured. The resultant colourant dispersion is continuously drawn offfrom the mixing nozzle and the colourant separated by filtration.

Finally, the coupling can also be carried out by suspending the amine tobe diazotised with the coupling component in the molar ratio 1:1 in anorganic solvent and treating the coupling mixture with a diazotisingagent, in particular an ester of nitrous acid, such as methyl, ethyl,butyl, amyl or octyl nitrite.

The azocarboxylic acid on which the halide of the formula IX is based isobtained by coupling the diazo compound of an amine of the formula Xwith a hydroxynaphthoic acid of the formula ##STR15##

The resultant azo dyestuff carboxylic acids are treated with agentswhich are capable of converting carboxylic acids into their halides, forexample the chlorides or bromides, in particular with phosphorushalides, such as phorphorus pentachloride or phosphorus trichloride orpentabromide, phosphoroxy halides and preferably with thionyl chloride.

The treatment with such acid halogenating agents is preferably carriedout in inert organic solvents, such as dimethyl formamide,chlorobenzenes, for example mono- or dichlorobenzene, toluene, xylene ornitrobenzene. In the case of these five last mentioned solvents,dimethyl formamide is optionally added.

In the preparation of the carboxylic acid halides, it is usuallyadvantageous to dry the azo compounds obtained in aqueous mediumbeforehand or to free them from water azeotropically by boiling them inan organic solvent. The azeotropic drying can be carried out, ifdesired, directly before the treatment with the acid halogenatingagents.

The condensation between the carboxylic acid halides of the kindmentioned at the outset and the aromatic diamines is expediently carriedout in anhydrous medium. Under this condition, the condensation takesplace as a rule with surprising ease at temperatures which lie in theboiling range of the normal organic solvents, for example, toluene,monochlorobenzene, dichlorobenzene, trichlorobenzene or nitrobenzene. Inorder to hasten the reaction it is in general advisable to use an acidacceptor, for example anhydrous sodium acetate or pyridine. Theresulting pigments are partly crystalline and partly amorphous and areobtained in most cases in very good yield and in a pure state. It isadvisable to first precipitate the acid chlorides obtained from thecarboxylic acids. In many cases, however, precipitation of the acidchloride can without detriment be dispensed with and the condensationcarried out directly after the manufacture of the carboxylic acidchlorides.

The pigments of the present invention can be used partly as crudeproducts. If desired, however, the crude products can be converted intoa finely dispersed form by grinding or kneading, advantageously usinggrinding assistants, such as inorganic and/or organic salts in thepresence or absence of organic solvents. After the grinding procedure,the assistants are removed in the conventional manner: soluble inorganicsalts for example with water, and water-insoluble assistants for exampleby steam distillation. The properties of the crude pigments can often beimproved by treating them with organic solvents, preferably those havinga boiling point above 100° C. Particularly suitable organic solventsare: benzenes which are substituted by halogen atoms, alkyl or nitrogroups, for example xylenes, chlorobenzene, o-dichlorobenzene ornitrobenzene, as well as pyridine bases, such as pyridine, picoline orquinoline, and also ketones, for example, cyclohexanone; ethers, forexample ethylene glycol monomethyl or monoethyl ether; amides, such asdimethyl formamide or N-methylpyrrolidone, as well as dimethylsulphoxide, sulpholane or water alone, with or without pressure. Theaftertreatment can also be carried out in water in the presence oforganic solvents and/or with the addition of surface-active substances.

The aftertreatment is effected preferably by heating the pigment in thesolvent to 100° to 200° C., whereupon in certain cases an increase inthe granular size and, in appropriate circumstances, a change in thecrystal modification, occurs. The fastness to light and migration of theresultant pigments are thereby favourably influenced.

The pigments obtained according to the invention are suitable forcolouring organic material of high molecular weight of natural orsynthetic origin. Such material can comprise for example natural resins,drying oils or rubber. However, it can also comprise modified naturalmaterials, for example chlorinated rubber, oil-modified alkyd resins orviscose or cellulose derivatives, such as acetyl cellulose andnitrocellulose, and in particular man-made organic polyplastics, that isto say, plastics which are obtained by polymerisation, polycondensationand polyaddition. The following products may be mentioned in particularas belonging to this class of plastics: polyethylene, polypropylene,polyisobutylene, polystyrene, polyvinyl chloride, polyvinyl acetate,polyacrylonitrile, polyacrylates, polymethacrylates; polyesters, inparticular esters of high molecular weight of aromatic polycarboxylicacids and polyfunctional alcohols; polyamides, the condensation productsof formaldehyde and phenols (phenolic plastics), and the condensationproducts of formaldehyde and urea, thiourea and melamine (aminoplasts);the polyesters used as varnish gums, namely both saturated polyesters,for example alkyd resins, and unsaturated polyesters, for example maleicresins, and also the polyaddition and polycondensation products ofepichlorohydrin and polyols or polyphenols known as epoxide resins; inaddition thermoplasts, i.e. the non-curable polyplastics. It must beemphasised that not only the homogeneous compounds can be pigmentedaccording to the invention, but also mixtures of polyplastics, as wellas co-condensates and copolymers, for example those based on butadiene.

The pigments of the present invention are particularly suitable forcolouring polyplastics, such as the film formers or binders known asvehicles, especially for colouring boiled linseed oil, nitrocellulose,alkyd resins, melamine resins and ure-formaldehyde resins. Thepigmenting of the organic substances of high molecular weight with thepigments of the formula (I) is effected for example by mixing such apigment, optionally in the form of masterbatches, with these substratesusing roll mills, mixing or grinding devices. The pigmented material isthereafter brought into the desired final form by known processes, suchas calendering, pressing, extruding, coating, casting, or by injectionmoulding. It is often desirable to add plasticisers to the compound ofhigh molecular weight before forming them in order to obtain non-rigidmoulded articles or to diminish their brittleness. Examples of suchplasticisers are esters of phosphoric acid, phthalic acid or sebacicacid. The plasticisers can be added in the process of the inventionbefore or after the incorporation of the pigment dye in thepolyplastics. In order to obtain different shades it is also possible toadd, in addition to the compounds of the formula (I), fillers or othercolouring constituents, such as white, coloured or black pigments, inany amounts to the organic substances.

For pigmenting lacquers and printing inks, the organic materials of highmolecular weight and the compounds of the formula (I), optionallytogether with additives, such as fillers, other pigments, siccatives orplasticisers, are finely dispersed or dissolved in a joint organicsolvent or solvent mixture. The procedure can consist for example indispersing or dissolving each of the components individually or alsoseveral jointly, and only thereafter combining all the components.

The pigmented organic materials of high molecular weight containnormally amounts from 0.001 to 30% by weight of a compound of theformula (I), based on the organic substance of high molecular weight tobe pigmented, Polyplastics and lacquers contain preferably 0.1 to 5% byweight, and printing inks contain preferably 10 to 30% by weight. Theamount of pigment to be chosen depends primarily on the desired colourstrength, on the layer thickness of the moulded article, and finallyalso on the content of white pigment, if any, in the polyplastic.

The colourants of the present invention are distinguished by their easyaccessibility, and by their good fastness to heat, light, overstripebleeding, migration and good resistance to atmospheric influences. Inspite of the high molecular weight of the diazo bases, and in comparisonto diazo bases of lower molecular weight, the pigments of the presentinvention have a high colour strength.

Compared with similar pigments described for example in GermanAuslegeschrift 1,816,990 and German Offenlegungsschrift 1,644,226, thepigments of the present invention are distinguished by better lightfastness and fastness to atmospheric influences.

In the following Examples which illustrate the invention the parts andpercentages are by weight unless otherwise stated.

EXAMPLE 1

31.3 parts of 4-methyl-3-aminobenzoic acid 4'-propoxycarbonylphenylester are stirred at room temperature in 200 parts by volume of glacialacetic acid. After about 5 minutes, 25 parts by volume of concentratedhydrochloric acid are added to the completely clear solution. Thesolution is cooled to 0° C. with ice, treated at 0°-5° C. with 25.5parts by volume of 4 N sodium nitrite solution over the course of 15minutes, and then diluted with 150 parts by volume of ice-water. Afterstirring for about 1 hour at 0°-5° C., excess nitrite is completelydestroyed with sulphamic acid and the reaction mixture is then filteredclear. 31.9 parts of 5-(2'-hydroxy-3'-naphthoylamino)-benzimidazoloneare dissolved at room temperature in 20 parts by volume of 30% sodiumhydroxide solution and 350 parts by volume of water. Two parts of Hyfloare then added to the solution, which is subsequently filtered clear. Tothe coupling solution are then added 7.5 parts by volume of 30%hydrochloric acid and then, in addition, 20 parts of calcined sodiumcarbonate. The diazo solution is added to the coupling component at15°-20° C. in the course of about 30 minutes. When the addition of diazosolution is complete, the pH falls from 12.2 to 3.9. The batch isstirred for 6 to 8 hours at 20°-25° C., then heated to 80° C. Thepigment is filtered off hot, washed with hot water and then with coldisopropanol. The filter cake is dried in vacuo at 70°-80° C., affording50 parts (97.5% of theory) of a reddish brown powder of the formula##STR16## which colours PVC in red shades.

A change in crystal modification occurs after an aftertreatment indimethyl formamide or N-methyl-2-pyrrolidone (30 minutes at boilingtemperature), yielding a pigment which colours PVC in a bright, redshade of very good fastness to migration and light and very goodresistance to atmospheric influences. The same results are also obtainedby heating the crude pigment for 6 hours in water with 1% of acondensation product of 20 moles of ethylene oxide and 1 mole of oleylalcohol, at 150° C. under pressure.

Table 1 lists further pigments which are obtained by coupling the diazocompound of the amine of column I with the 2-hydroxy-3-naphthoic arylidecompound of column II and by a subsequent aftertreatment in the solventindicated in column IV. Column III indicates the shade in which PVC iscoloured with 0.2% of these pigments. The abbreviations NMP and DMFA incolumn IV denote N-methyl-2-pyrrolidone and dimethyl formamiderespectively.

                                      TABLE 1                                     __________________________________________________________________________    Ex-                                                                           ample                                                                             Diazo component  Coupling component                                                                          Shade                                                                             Solvent                                __________________________________________________________________________    2   3-amino-4-methoxybenzoic acid                                                                  5-(2'-hydroxy-3'-naphthoyl-                                                                 red DMFA                                       3'-isopropoxycarbonylphenyl ester                                                              amino)-benzimidazolone                                   3   3-amino-4-chlorobenzoic acid 4'-                                                               5-(2'-hydroxy-3'-naphthoyl-                                                                 reddish                                                                           DMFA                                       isopropoxycarbonyl phenyl ester                                                                amino)-benzimidazolone                                                                      brown                                      4   3-amino-4-methylbenzoic acid                                                                   5-(2'-hydroxy-3'-naphthoyl-                                                                 violet                                                                            NMP                                        α-naphthyl ester                                                                         amino)-benzimidazolone                                                                      brown                                      5   3-amino-4-methylbenzoic acid β-                                                           5-(2'-hydroxy-3'-naphthoyl-                                                                 red NMP                                        chloroethyl ester                                                                              amino)-benzimidazolone                                   6   3-amino-4-methylbenzoic acid 4'-                                                               5-(2'-hydroxy-3'-naphthoyl-                                                                 red NMP                                        chlorophenyl ester                                                                             amino)-benzimidazolone                                   7   3-amino-4-methylbenzoic acid 4'-                                                               5-(2'-hydroxy-39-naphthoyl-                                                                 red NMP                                        propoxycarbonylphenyl ester                                                                    amino)-6-chlorobenzimida-                                                     zolone                                                   8   3-amino-4-methoxybenzoic acid 3'-                                                              5-(2'-hydroxy-39-naphthoyl-                                                                 red NMP                                        isopropoxycarbonylphenyl ester                                                                 amino)-6-chlorobenzimida-                                                     zolone                                                   9   3-amino-4-chlorobenzoic acid 4'-                                                               5-(2'-hydroxy-39-naphthoyl-                                                                 red DMFA                                       isopropoxycarbonylphenyl ester                                                                 amino)-6-chlorobenzimida-                                                     zolone                                                   10  3-amino-4-methylbenzoic acid α-                                                          5-(2'-hydroxy-39-naphthoyl-                                                                 red NMP                                        naphthyl ester   amino)-6-chlorobenzimida-                                                     zolone                                                   11  3-amino-4-methylbenzoic acid β-                                                           5-(2'-hydroxy-39-naphthoyl-                                                                 red NMP                                        chloroethyl ester                                                                              amino)-6-chlorobenzimida-                                                     zolone                                                   12  3-amino-4-methylbenzoic acid 4'-                                                               5-(2'-hydroxy-39-naphthoyl-                                                                 red NMP                                        chlorophenyl ester                                                                             amino)-6-chlorobenzimida-                                                     zolone                                                   13  3-amino-4-methylbenzoic acid 4'-                                                               5-(2'-hydroxy-3'-naphthoyl                                                                  red NMP                                        propoxycarbonylphenyl ester                                                                    amino)-6-methylbenzimida-                                                     zolone                                                   14  3-amino-4-methoxybenzoic acid                                                                  5-(2'-hydroxy-3'-napthoyl-                                                                  violet                                                                            NMP                                        3'-isopropoxycarbonylphenyl ester                                                              amino)-6-methylbenzimida-                                                                   brown                                                           zolone                                                   15  3-amino-4-chlorobenzoic acid 4'-                                                               5-(2'-hydroxy-3'-napthoyl-                                                                  reddish                                                                           NMP                                        isopropoxycarbonylphenyl ester                                                                 amino)-6-methylbenzimida-                                                                   brown                                                           zolone                                                   16  3-amino-4-methylbenzoic acid β-                                                           5-(2'-hydroxy-3'-napthoyl-                                                                  red NMP                                        chloroethyl ester                                                                              amino)-6-methylbenzimida-                                                     zolone                                                   17  3-amino-4-methylbenzoic acid 4'-                                                               5-(2'-hydroxy-3'-napthoyl-                                                                  red NMP                                        chlorophenyl ester                                                                             amino)-6-methylbenzimida-                                                     zolone                                                   18  3-amino-4-methylbenzoic acid 4'-                                                               1-N-methyl-5-(2'-hydroxy-                                                                   red DMFA                                       propoxycarbonylphenyl ester                                                                    3'-naphthoylamino)-benzimi-                                                   dazolone                                                 19  3-amino-4-methoxybenzoic acid 3'-                                                              1-N-methyl-5-(2'-hydroxy-                                                                   red DMFA                                       isopropoxycarbonylphenyl ester                                                                 3'-naphthoylamino)-benzimi-                                                   dazolone                                                 20  3-amino-4-chlorobenzoic acid 4'-                                                               1-N-methyl-5-(2'-hydroxy-                                                                   red DMFA                                       isopropoxycarbonylphenyl ester                                                                 3'-naphthoylamino)-benzimi-                                                   dazolone                                                 21  3-amino-4-methylbenzoic acid β-                                                           1-N-methyl-5-(2'-hydroxy-                                                                   red DMFA                                       chloroethyl ester                                                                              3'-naphthoylamino)-benzimi-                                                   dazolone                                                 22  3-amino-4-methylbenzoic acid 4'-                                                               1-N-methyl-5-(2'-hydroxy-                                                                   red NMP                                        chlorophenyl ester                                                                             3'-naphthoylamino)-benzimi-                                                   dazolone                                                 23  3-amino-4-methylbenzoic acid                                                                   5-(2'-hydroxy-3'-naphthoyl-                                                                 red NMP                                        isopropyl ester  amino)-benzimidazolone                                   24  3-amino-4-methylbenzoic acid                                                                   5-(2'-hydroxy-3'-naphthoyl-                                                                 red NMP                                        isopropyl ester  amino)-6-chlorobenzimida-                                                     zolone                                                   25  3-amino-4-methylbenzoic acid                                                                   5-(2'-hydroxy-3'naphthoyl                                                                   red DMFA                                       isopropyl ester  amino)-6-methylbenzimida-                                                     zolone                                                   26  3-amino-4-methylbenzoic acid                                                                   1-N-methyl-5-(2'-hydroxy-3'-                                                                red DMFA                                       isopropyl ester  naphthoylamino)-benzimida-                                                    zolone                                                   __________________________________________________________________________

EXAMPLE 27

15.4 parts of the azo dye obtained from diazotised4-methyl-3-aminobenzoic acid 4'-propoxycarbonylphenyl ester and2-hydroxy-3-naphthoic acid are suspended in 50 parts ofo-dichlorobenzene. 5 parts of thionyl chloride and 0.05 part of pyridineare added to the mixture, which is heated to 95° C. and stirred for 11/2hours at 95°-100° C. The crystalline compound is filtered cold bysuction and dried in vacuo at 70°-75° C., affording 14 parts of theazocarboxylic chloride of the formula ##STR17##

5.31 parts of the above acid chloride are heated, with stirring, in 100parts of o-dichlorobenzene to 110°-120° C. Then a warm solution of 100°C. containing 1.6 parts of 5-aminobenzimidazolone in 10 parts ofN-methyl-2-pyrrolidone and 25 parts of o-dichlorobenzene is added in thecourse of 2 to 3 minutes. The precipitated pigment is stirred for 16hours at 140°-145° C. The reaction mixture is filtered hot, and thefilter cake is washed with hot o-dichlorobenzene, then with methanol andfinally with water, then dried in vacuo at 60°-70° C., affording 4.3parts of a soft-grained brown pigment powder which colours plastics, forexample polyvinyl chloride, as well as lacquers, in red shades ofexcellent fastness to migration, overstripe bleeding and light. Thepigment dye has the following structural formula ##STR18##

Table 2 lists further acid amide derivative of azo dyes which areobtained by condensing, in accordance with the particulars of thisExample, 1 molecule of the acid chloride of the azo compound of thediazo component in column I and of the coupling component listed incolumn II with 1 mole of the amine in column III. Column IV indicatesthe shades of a polyvinyl chloride sheet coloured with the correspondingpigment.

                                      TABLE 2                                     __________________________________________________________________________    Ex-                                                                           ample                                                                             I              II      III          IV                                    __________________________________________________________________________    28  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          4-methyl-7,8-benzo-6-                                                                      bluish red                                4'-propoxycarbonylphenyl ester                                                               naphtholic acid                                                                       aminoquinolone-(2)                                 29  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-6-methoxy-                                                                         reddish brown                             4'-propoxycarbonylphenyl ester                                                               naphthoic acid                                                                        benzimidazolone                                    30  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-6-ethoxy-                                                                          reddish brown                             4'-propoxycarbonylphenyl ester                                                               naphthoic acid                                                                        benzimidazolone                                    31  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-7-methyl-                                                                          red                                       4'-propoxycarbonylphenyl ester                                                               naphthoic acid                                                                        benzimidazolone                                    32  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          1-N-ethyl-5-amino-                                                                         red                                       4'propoxycarbonylphenyl ester                                                                naphthoic acid                                                                        benzimidazolone                                    33  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          1-N-propyl-5-amino-                                                                        red                                       4'-propoxycarbonylphenyl ester                                                               naphthoic acid                                                                        benzimidazolone                                    34  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          7-amino-6-chlorophen-                                                                      red                                       4'-chlorophenyl ester                                                                        naphthoic acid                                                                        morpholone-(3)                                     35  3-amino-4-methylbenzoic acid                                                                 2,3-hydroxy-                                                                          7-amino-6-methylphen-                                                                      reddish brown                             4'-chlorophenyl ester                                                                        naphthoic acid                                                                        morpholone-(3)                                     36  2-amino-benzoic acid 4'-                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       chlorophenyl ester                                                                           naphthoic acid                                             37  3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          brown                                     propyl ester   naphthoic acid                                                                        benzimidazolone                                    38  3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     brown                                     propyl ester   naphthoic acid                                             39  3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid propyl ester                                                                            naphthoic acid                                             40  3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       acid propyl ester                                                                            naphthoic acid                                                                        benzimidazolone                                    41  3-amino-4-methylbenzoic                                                                      2,3-hydroxy-                                                                          5-amino-benzimida-                                                                         red                                       acid propyl ester                                                                            naphthoic acid                                                                        zolone                                             42  3-amino-4-methylbenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-methyl-                                                                          bluish red                                acid n-butyl ester                                                                           naphthoic acid                                                                        benzimidazolone                                    43  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          5-amino-benzimida-                                                                         red                                       sulphonic acid 4'-chloro-                                                                    naphthoic acid                                                                        zolone                                                 phenyl ester                                                              44  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       sulphonic acid 4'-chloro-                                                                    naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              45  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          7-amino-6-methyl-                                                                          red                                       sulphonic acid 4'-chloro                                                                     naphthoic acid                                                                        phenmorpholone-(3)                                     phenyl ester                                                              46  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          5-amino-benzimida-                                                                         red                                       sulphonic acid 4'-methyl-                                                                    naphthoic acid                                                                        zolone                                                 phenyl ester                                                              47  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       sulphonic acid 4'-methyl-                                                                    naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              48  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          5-amino-benzimida-                                                                         red                                       sulphonic acid 4'-methoxy-                                                                   naphthoic acid                                                                        zolone                                                 phenyl ester                                                              49  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          5-amino-6-methyl-                                                                          red                                       sulphonic acid 4'-methoxy-                                                                   naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              50  3-amino-4-methoxybenzene-                                                                    2,3-hydroxy-                                                                          5-amino-6-methoxybenz-                                                                     reddish brown                             sulphonic acid 4'-methoxy-                                                                   naphthoic acid                                                                        imidazolone                                            phenyl ester                                                              51  4-chloro-3-aminobenzoic acid                                                                 2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     reddish brown                             3',5'-dimethylphenyl ester                                                                   naphthoic acid                                             52  4-chloro-3-aminobenzoic acid                                                                 2,3-hydroxy-                                                                          6-methyl-5-amino-                                                                            "                                       3',5'-dimethylphenyl ester                                                                   naphthoic acid                                                                        benzimidazolone                                    53  4-chloro-3-aminobenzoic acid                                                                 2,3-hydroxy-                                                                          6-methoxy-5-amino-                                                                         brown                                     3',5'-dimethylphenyl ester                                                                   naphthoic acid                                                                        benzimidazolone                                    54  4-chloro-3-aminobenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-1-methyl-                                                                          red                                       3',5'-dimethylphenyl ester                                                                   naphthoic acid                                                                        benzimidazolone                                    55  4-chloro-3-aminobenzoic acid                                                                 2,3-hydroxy-                                                                          7-amino-6-methyl-                                                                          red                                       3',5'-dimethylphenyl ester                                                                   naphthoic acid                                                                        phenmorpholone-3                                   56  4-methoxy-3-aminobenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     bluish red                                acid β-chloroethyl ester                                                                naphthoic acid                                             57  4-methoxy-3-aminobenzoic                                                                     2,3-hydroxy-                                                                          5-chloro-5-aminobenz-                                                                        "                                       acid β-chloroethyl ester                                                                naphthoic acid                                                                        imidazolone                                        58  4-methoxy-3-aminobenzoic                                                                     2,3-hydroxy-                                                                          6-methyl-5-aminobenz-                                                                        "                                       acid β-chloroethyl ester                                                                naphthoic acid                                                                        imidazolone                                        59  4-(4'-chlorophenoxy)-3-amino-                                                                2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       benzoic acid 4"-chlorophenyl                                                                 naphthoic acid                                                 ester                                                                     60  4-(4'-chlorophenoxy)-3-amino-                                                                2,3-hydroxy-                                                                          5-amino-1-methyl-                                                                          red                                       benzoic acid 4"-chlorophenyl                                                                 naphthoic acid                                                                        benzimidazolone                                        ester                                                                     61  4-methoxy-3-aminobenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid 3',5'-dichlorophenyl                                                                    naphthoic acid                                                 ester                                                                     62  2-aminoterephthalic acid                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     brown                                     dimethyl ester naphthoic acid                                             63  2-aminoterephthalic acid                                                                     2,3-hydroxy-                                                                          6-methyl-5-amino-                                                                            "                                       dimethyl ester naphthoic acid                                                                        benzimidazolone                                    64  4-methyl-3-aminobenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzoimidazolone                                                                    red                                       acid 3',5'-dimethylphenyl                                                                    naphthoic acid                                                 ester                                                                     65  4-methyl-3-aminobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-1-methyl-                                                                          red                                       acid 3',5'-dimethylphenyl                                                                    naphthoic acid                                                                        benzimidazolone                                        ester                                                                     66  4-methyl-3-aminobenzoic                                                                      2,3-hydroxy-                                                                          6-methyl-7-amino-                                                                          red                                       acid 3',5'-dimethylphenyl                                                                    naphthoic acid                                                                        phenmorpholone-3                                       ester                                                                     67  4-chloro-3-aminobenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     brown                                     acid 2-naphthyl ester                                                                        naphthoic acid                                             68  4-chloro-3-aminobenzoic                                                                      2,3-hydroxy-                                                                          6-methyl-5-aminobenz-                                                                      reddish brown                             acid 2-naphthyl ester                                                                        naphthoic acid                                                                        imidazolone                                        69  4-chloro-3-aminobenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     brown                                     acid 2-naphthyl ester                                                                        naphthoic acid                                             70  4-chloro-3-aminobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-1-methyl-                                                                          scarlet                                   acid-2-naphthyl ester                                                                        naphthoic acid                                                                        benzimidazolone                                    71  4-methoxy-3-aminobenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid β-phenylethyl ester                                                                naphthoic acid                                             72  4-methoxy-3-aminobenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     bluish red                                acid 2',5'-dichlorophenyl                                                                    naphthoic acid                                                 ester                                                                     73  4-methoxy-3-aminobenzene                                                                     2,3-hydroxy-                                                                              "        violet                                    sulphonic acid phenyl ester                                                                  naphthoic acid                                             74  4-methoxy-3-aminobenzene                                                                     6-methoxy-2,3-                                                                            "          "                                       sulphonic acid phenyl ester                                                                  hydroxynaph-                                                                  thoic acid                                                 75  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                              "        brown                                     acid β-ethoxyethyl ester                                                                naphthoic acid                                             76  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                        "                                       acid β-ethoxyethyl ester                                                                naphthoic acid                                                                        imidazolone                                        77  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid 4'-chlorophenyl ester                                                                   naphthoic acid                                             78  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       acid 4'-chlorophenyl ester                                                                   naphthoic acid                                                                        benzimidazolone                                    79  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-methyl-                                                                          brown                                     acid 4'-chlorophenyl ester                                                                   naphthoic acid                                                                        benzimidazolone                                    80  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          4-methyl-6-amino-7-                                                                        red                                       acid 4'-chlorophenyl ester                                                                   naphthoic acid                                                                        chloroquinolone                                    81  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          7-amino-phenmorpholone-3                                                                   brown                                     acid 4'-chlorophenyl ester                                                                   naphthoic acid                                             82  3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid 4'-chlorophenyl ester                                                                   naphthoic acid                                             83  3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      red                                       acid 4'-chlorophenyl ester                                                                   naphthoic acid                                                                        imidazolone                                        84  3-amino-benzoic acid phenyl                                                                  2,3-hydroxy-                                                                          5-amino-6-chlorobenz-                                                                      red                                       ester          naphthoic acid                                                                        imidazolone                                        85  3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid phenyl ester                                                                            naphthoic acid                                             86  3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      red                                       acid phenyl ester                                                                            naphthoic acid                                                                        imidazolone                                        87  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          5-amino-6-chlorobenz-                                                                      red                                       sulphonic acid phenyl ester                                                                  naphthoic acid                                                                        imidazolone                                        88  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          7-amino-6-methyl-                                                                          red                                       sulphonic acid phenyl ester                                                                  naphthoic acid                                                                        phenmorpholone-3                                   89  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          7-aminophenmorpholone-3                                                                    red                                       sulphonic acid phenyl ester                                                                  naphthoic acid                                             90  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       sulphonic acid 4'-chloro-                                                                    naphthoic acid                                                 phenyl ester                                                              91  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          5-amino-6-chlorobenz-                                                                      red                                       sulphonic acid 4'-chloro-                                                                    naphthoic acid                                                                        imidazolone                                            phenyl ester                                                              92  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          5-amino-1-methylbenz-                                                                      red                                       sulphonic acid 4'-chloro-                                                                    naphthoic acid                                                                        imidazolone                                            phenyl ester                                                              93  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       sulphonic acid 4'-methyl-                                                                    naphthoic acid                                                 phenyl ester                                                              94  3-amino-4-methylbenzene-                                                                     2,3-hydroxy-                                                                          5-amino-6-chlorobenz-                                                                      red                                       sulphonic acid 4'-methyl-                                                                    naphthoic acid                                                                        imidazolone                                            phenyl ester                                                              95  3-amino-4-methylbenzene                                                                      2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      red                                       sulphonic acid 4'-methyl-                                                                    naphthoic acid                                                                        imidazolone                                            phenyl ester                                                              96  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      brown                                     acid methyl ester                                                                            naphthoic acid                                                                        imidazolone                                        97  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     brown                                     acid methyl ester                                                                            naphthoic acid                                             98  3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-chlorobenz-                                                                      brown                                     acid methyl ester                                                                            naphthoic acid                                                                        imidazolone                                        99  3-amino-4-methylbenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid methyl ester                                                                            naphthoic acid                                             100 3-amino-4-methylbenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-methoxy-                                                                         claret                                    acid methyl ester                                                                            naphthoic acid                                                                        benzimidazolone                                    101 3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid methyl ester                                                                            naphthoic acid                                             102 3-amino-4-methoxybenzoic                                                                     2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      red                                       acid methyl ester                                                                            naphthoic acid                                                                        imidazolone                                        103 3-amino-4-methylbenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      red                                       acid ethyl ester                                                                             naphthoic acid                                                                        imidazolone                                        104 3-amino-4-methylbenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid ethyl ester                                                                             naphthoic acid                                             105 3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                              "        brown                                     acid ethyl ester                                                                             naphthoic acid                                             106 3-amino-4-chlorobenzoic                                                                      2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      brown                                     acid ethyl ester                                                                             naphthoic acid                                                                        imidazolone                                        107 3-amino-4-methylbenzoic                                                                      2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid phenyl ester                                                                            naphthoic acid                                             108 3-amino-4,6-dichlorobenzoic                                                                  2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid phenyl ester                                                                            naphthoic acid                                             109 3-amino-4,6-dichlorobenzoic                                                                  2,3-hydroxy-                                                                          5-amino-6-methyl-                                                                          brown                                     acid phenyl ester                                                                            naphthoic acid                                                                        benzimidazolone                                    110 3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-6-methyl-                                                                          red                                       4'-carbomethoxyphenyl ester                                                                  naphthoic acid                                                                        benzimidazolone                                    111 3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     brown                                     4'-carbomethoxyphenyl ester                                                                  naphthoic acid                                             112 3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       4'-carbomethoxyphenyl ester                                                                  naphthoic acid                                                                        benzimidazolone                                    113 3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       4'-carboethoxyphenyl ester                                                                   naphthoic acid                                                                        benzimidazolone                                    114 3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     brown                                     4'-carboethoxyphenyl ester                                                                   naphthoic acid                                             115 3-amino-4-chlorobenzoic acid                                                                 2,3-hydroxy-                                                                          5-amino-1-methylbenz-                                                                      red                                       4'-carboethoxyphenyl ester                                                                   naphthoic acid                                                                        imidazolone                                        116 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid β-chloroethyl ester                                                                naphthoic acid                                             117 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       acid β-chloroethyl ester                                                                naphthoic acid                                                                        benzimidazolone                                    118 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      claret                                    acid β-chloroethyl ester                                                                naphthoic acid                                                                        imidazolone                                        119 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          6-amino-2,4-dioxy-                                                                         orange                                    acid β-chloroethyl ester                                                                naphthoic acid                                                                        quinazoline                                        120 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          7-amino-6-methyl-phen-                                                                     claret                                    acid β-chloroethyl ester                                                                naphthoic acid                                                                        morpholone-(3)                                     121 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          4-methyl-6-amino-7-                                                                        orange                                    acid β-chloroethyl ester                                                                naphthoic acid                                                                        choroquinolone-2                                   122 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid 4'-methoxyphenyl ester                                                                  naphthoic acid                                             123 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       acid 4'-methoxyphenyl ester                                                                  naphthoic acid                                                                        benzimidazolone                                    124 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-methyl-                                                                          brown                                     acid 4'-methoxyphenyl ester                                                                  naphthoic acid                                                                        benzimidazolone                                    125 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          7-amino-6-methyl-                                                                          scarlet                                   acid 4'-methoxyphenyl ester                                                                  naphthoic acid                                                                        phenmorpholone-(3)                                 126 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     red                                       acid 3'-trifluoromethyl-                                                                     naphthoic acid                                                 phenyl ester                                                              127 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       acid 3'-trifluoromethyl-                                                                     naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              128 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-methyl-                                                                          red                                       acid 3'-trifluoromethyl-                                                                     naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              129 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-methoxy-                                                                         red                                       acid 3'-trifluoromethyl-                                                                     naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              130 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          1-methyl-5-amino-                                                                          bluish red                                acid 3'-trifluoromethyl-                                                                     naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              131 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          7-amino-6-chlorophen-                                                                      orange                                    acid 3'-trifluoromethyl-                                                                     naphthoic acid                                                                        morpholone-(3)                                         phenyl ester                                                              132 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          7-amino-6-methyl-phen-                                                                     claret                                    acid 3'-trifluoromethyl-                                                                     naphthoic acid                                                                        morpholone-(3)                                         phenyl ester                                                              133 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     claret                                    acid 4'-carbomethoxy-                                                                        naphthoic acid                                                 phenyl ester                                                              134 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-chlorobenz-                                                                      claret                                    acid 4'-carbomethoxy-                                                                        naphthoic acid                                                                        imidazolone                                            phenyl ester                                                              135 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-methylbenz-                                                                      claret                                    acid 4'-carbomethoxy-                                                                        naphthoic acid                                                                        imidazolone                                            phenyl ester                                                              136 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-methoxy-                                                                         brown                                     acid 4'-carbomethoxy-                                                                        naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              137 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          1-Methyl-5-amino-                                                                          bluish red                                acid 4'-carbomethoxy-                                                                        naphthoic acid                                                                        benzimidazolone                                        phenyl ester                                                              138 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          7-amino-6-chlorophen-                                                                      bluish red                                acid 4'-carbomethoxy-                                                                        naphthoic acid                                                                        morpholone-(3)                                         phenyl ester                                                              139 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          7-amino-6-methylphen-                                                                      claret                                    acid 4'-carbomethoxy-                                                                        naphthoic acid                                                                        morpholone-(3)                                         phenyl ester                                                              140 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          7-aminophenmorpholone-                                                                     bluish red                                acid 4'-carbomethoxy                                                                         naphthoic acid                                                                        (3)                                                    phenyl ester                                                              141 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-aminobenzimidazolone                                                                     claret                                    acid β-naphthyl ester                                                                   naphthoic acid                                             142 1-amino-2-methyl-5-benzoic                                                                   2,3-hydroxy-                                                                          5-amino-6-chloro-                                                                          red                                       acid β-naphthyl ester                                                                   naphthoic acid                                                                        benzimidazolone                                    143 1-amino-2-methyl-5-benzoic                                                                   6-methoxy-2,3-                                                                        5-aminobenzimidazolone                                                                     bluish red                                acid ethyl ester                                                                             hydroxy-                                                                      naphthoic acid                                             __________________________________________________________________________

EXAMPLE 144

0.6 g of the pigment obtained in Example 1 is mixed with 67 g ofpolyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyl tindilaurate and 2 g of titanium dioxide and the mixture is processed to athin sheet for 15 minutes at 160° C. on a roll mill. The red colourationobtained is strong and fast to migration and light.

EXAMPLE 145

1 g of pigment obtained in Example 1 is finely ground in an Engelsmanngrinding machine with 4 g of a litho varnish of the composition:

29.4% of linseed oil-stand oil (300 poise)

67.2% of linseed oil-stand oil (20 poise)

2.1% of cobalt octoate (8% Co) and

1.3% of lead octoate (24% Pb).

Using a stereotype block, this varnish is printed in an amount of 1 g/m²on art paper by letterpress printing. A strong, bright, red shade ofgood transparence and good gloss is obtained.

The pigment is also suitable for other printing methods, such asintaglio printing, offset printing, flexographic printing, with equallygood results.

EXAMPLE 146

15 g of collodion cotton containing 35% of butanol, 15 g of a phthalateresin modified with castor oil, 15 g of a 70% butanolic solution of aurea varnish gum, 20 g of butyl acetate, 10 g of glycol monoethyl ether,20 g of toluene and 5 g of alcohol are processed to a lacquer. Thislacquer is then pigmented with 2 g of the colourant of Example 1 and 2 gof titanium dioxide (rutile) and ground. The lacquer is sprayed ontocardboard and dried, giving a red coating of very good fastness to lightand overstripe bleeding and very good resistance to atmosphericinfluences.

EXAMPLE 147

To 100 g of a stoving lacquer consisting of 58.5 g of a 60% solution ofa coconut alkyd resin in xylene, 23 g of a 65% solution of a melaminevarnish gum in butanol, 17 g of xylene and 1.5 g of butanol, are added 1g of the colourant of Example 1 and 5 g of titanium dioxide. The mixtureis ground for 48 hours in a ball mill and the pigmented lacquer issprayed onto a clean metal surface. After stoving at 120° C., a redcolouration of good fastness to light and overstripe bleeding and goodresistance to atmospheric influences is obtained.

What is claimed is:
 1. A monoazo pigment of the formula ##STR19##wherein Z represents --CO-- or --SO₂ --,Q represents hydrogen, bromineor methoxy, Y₁ represents hydrogen, chlorine, alkyl of 1 to 4 carbonatoms or alkoxy of 1 to 4 carbon atoms, Y₂ and Y₃ independentlyrepresent a hydrogen, chlorine, trifluoromethyl, alkyl of 1 to 4 carbonatoms, alkoxy of 1 to 4 carbon atoms, alkanoylamino of 2 to 4 carbonatoms or the --COOR₁, wherein R₁ represents alkyl of 1 to 4 carbon atomswhich is unsubstituted or substituted by halogen, alkoxy of 1 to 4carbon atoms; cycloalkyl of 5 to 6 carbon atoms; benzyl which isunsubstituted or substituted by halogen, alkyl of 1 to 4 carbon atoms oralkoxy of 1 to 4 carbon atoms; or phenyl which is unsubstituted orsubstituted by halogen, alkyl of 1 to 4 carbon atoms or alkoxy groups of1 to 4 carbon atoms, or Y₂ and Y₃ together with the carbon atoms towhich they are attached form benzene ring which is unsubstituted orsubstituted by chlorine, X₁ represents hydrogen, chlorine, an alkyl of 1to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to4 carbon atoms or phenoxy, R² represents hydrogen, alkyl of 1 to 4carbon atoms or phenyl which is unsubstituted or substituted by halogen,alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, X₂represents hydrogen, halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1to 4 carbon atoms or a phenoxy, and n is 1 or 2.with the proviso that ifR₂ represents alkyl or phenyl, at least one of Y₁, Y₂ or Y₃ may notrepresent hydrogen.
 2. A monoazo pigment according to claim 1 of theformula II ##STR20## wherein R₃ represents hydrogen or methyl,X₄represents chlorine, methyl, methoxy, methoxycarbonyl or ethoxycarbonyl,and X₅ represents hydrogen, chlorine, methyl or methoxy, with theproviso that, if R₃ is methyl, at least one of the symbols Y₁, Y₂ or Y₃may not represent hydrogen.
 3. A monoazo pigment according to claim 2 ofthe formula III ##STR21## wherein R₄ represents alkyl of 1 to 4 carbonatoms, benzyl which is unsubstituted or substituted by chlorine, alkylof 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; or phenyl whichis unsubstituted or substituted by chlorine alkyl of 1 to 4 carbonatoms, or alkoxy groups of 1 to 4 carbon atoms.
 4. A monoazo pigmentaccording to claim 2 of the formula IV ##STR22## wherein X₆ representsatom hydrogen or chlorine atom.
 5. The monoazo pigment according toclaim 1 of the formula ##STR23##
 6. The monoazo pigment according toclaim 1 of the formula ##STR24##
 7. The monoazo pigment according toclaim 1 of the formula ##STR25##